Azo dyestuff and process of making



Reissued Apr. 9, 1935 UNITED STATES PATENTS OFFICE 19,527 AZO DYESTUFFAND PROCESS orv MAKING SAME August Leopold Laska and Arthur Zitscher, f-

fenbach -,0'n the Main, Germany, assignors to I. G. FarbenindustrieAktiengesellschalt, Frankfort-on-the-Main, Germany No Drawing. OriginalNo. 1,457,114, dated May 29, 1923, Serial No. 611,503, January 8, 1923.Application for reissue August 28, 1932, Serial 3 (,laims.

aromatic amine in which the nucleus may be substituted by one ormoresubstituents selected from the group consisting of halogen, alkyl,alkoxy and nitro groups but which does not contain any group causingsolubility, such as the sulfonic acid or carboxylic acid group, with anothro-alkoxyarylide of the 2, 3-hydroxynaphthoic acid of the generalformula:

, COAQHQ Alkyl wherein the nucleus R may be substituted by a substituentselected from the group consisting of halogen, alkyl, alkoxy and nitrogroups.

The new dyestuiis are represented by the general formula:

wherein the nuclei R and R1 may be substituted by substituents selectedfrom the group consisting of halogen, alkyl, alkoxy and nitro groups.

The dyestuffs can be used for the production of color lakes of anexcellent fastness to light and give, when produced on the fiber, orangeto red and Bordeaux shades of asingularfastness tolight, they are whendry, orange to red and brownish powders, insoluble in water, soluble insulfuric acid to a violet to green solution yielding upon reduction withstannous chloride an amine and an ortho-alkoxyarylamide'of thel-amino-2-hydroxy-3-naphthoic acid. 1

The invention is illustrated by the following examples:

1'. A diazo-solution, prepared in the usual manner from 16.2 parts of2,5-dichloroaniline, is poured, while stirring well, into an aqueoussuspension of 30.7 parts of ortho-anisidide of the 2,3-

hydroxynaphthoic acid, prepared by dissolving it in dilute caustic sodalye and precipitating with dilute acetic acid. The dyestuff separates inbrightly reddish flakes, it is filtered, when the combination iscomplete, washed until neutral and advantageously used in the form of apaste. Mixed with the usual substrata it forms color lakes of anexcellent fastness to light.

The dyestufi has the following structural formula:

CHI.

Instead of ortho-anisidide we may use orthophenetidide of the2,3-hydroxynaphthoic acid.

2. PRODUCTION OF THE DYESTUFFS ON II-IE FIBER Padding bath 10 rams ofortho-anisidide of 2,3-hydroxynapht oic acid are well stirred with 20cc. of caustic soda lye of 34 B. and 20 cc. of Turkey red oil, dissolvedwith 200 cc. of hot water and made up to 1 liter.

The cotton goods, which are impregnated with this solution, are wellwrung out and then developed in the following:

3 grams of 4-chloro-1,2-toluidine are diazotized in the usual manner,the solution is diluted with cold water to I liter, neutralized withsodium acetate and 50 grams of common salt are added.

The dyed goods are rinsed, as usually, with cold and warm water, thensoaped, while boiling well, rinsed again and dried.

Printing-directions Printing-color 4500 cc. of the diazo solution,

4000 grams of tragacanth thickening 1:20, 1000 cc; of aluminium sulfate1:1, I

500 ec.-. of sodium: acetate 1 :1, 1 a.

by a substituent selected from the group consisting of halogen, alkyl,alkoxy and nitro groups.

2. The water-insoluble azo dyestuffs of the general formula: I

10 After printing the goods are dried-at 40 (Lto 5p? 0., soaped with awarm and fbly alkalifieso'lii x tion of soap and rinsed with hot water.

The following table gives the-tints o r =number of the dyestuffs,prepared according to the" present: 6 ONH@ process, and of the colorlakes obtained there from: m -1 Diazo compiflifidofz r I Combined with:Shades:

1 3-chloroaniline Ortho-anisidide of 2 fi-liydroxynaphthoic acid---Orange. 2 2-ch1oroaniline. a o Yellowish red. 3 2, -dicl1loroanilineYellowish red. 4 4-chloro-l, 2-toluidine. Red. 5 5-chlol'0-1; 2-toluldinBlulsli'red 6 6'chloro-1, Z-toluidin ed. 7 Yellowish red. 8 Bluish red.9 Bordeaux 10 Red. 11 Yellowish red 12 Bordeaux. 13 Bordeaux. 14Bordeaux. 15 3-nitro-l, 4-toluidiue Red.

16 40hl0lO-2-filti'0B-l1llltl8; Y Bluish red. 17 Dianisidine Reddishblue. 18 Ortho-phenetole-azo-a]pha-naphtliylamine Black. 19 4-cl1loro-l,2-toluidine d- 20 5-cl1loro-l, 2-toluidine Bluish red. 21 fi-chloro-l,2-toluidine Red; 22 2-chloro-l, 4-toluidine Red. 23 3-chloro-1, 4toliiidine. Red. 24 4-chl0ro-2-nitroan1line: Bluish red. 25 4-chloro-l,2-anisidine- Bordeaux. 26 5-chloro-1, 2-anisidine. Reddisli Bordeaux. 274-nitro-l, z-anisidine Bluish red. 28 E-nitro-l, Z-toluidine Red. 293-nitro l, 4=toluidjne Reddish Bordeaux. 30 m-aminoazptoluene Likegarnet. 31 5chloro-1, 2-toluid1'ne. Bluish red. 32 6-chloro-1,2-toluidilge Yellowish red. 33 4-chloro-l, Z-aniSidln. Bordeaux. 343-nitrol, 4-to1uidine Bordeaux. 35 S-nitro-l, 4-to1uidine. Bluish red. V36 5'-nitro-1, 2-anisldine; Reddish Bordeaux. 37 2, 5-dichlofoanilineYellowish red. 3s 3-nitro-l, 4-toluidine 'Blui s'h red. 39 5-nitro-l,2-toluidin 0.; Bordeaux. 40 2, S-diChIoib-aniline. 2,Flo-5ydroxynaphthoyl-3-ammo-l, 4-creso1ethyl- Yellowlsh red.

' e er. 41 3-nitro-l, 4-toluidine'. do Bluish red. 42 5-nitro-1,2-toluidine. do Bluish red. 43 4-nitro-l 2-anisidine. Red.

44 4-"chloio-l, 2-anlsidine 'Bluish red. 45 2, .5-dichloroaniline;Brownish orange.

Since an object of the present invention is; to provide dyestuffs ofgoodfastness properties, which dyestuffs are insoluble. in water and allkalies, it is to be understood 'tl'mt the aromatic nuclei of the generalformulae appearing in the appended claims do not contain anysubstituents which are known to render organic compounds soluble inwater or alkaliesand to tend to depreciate the fastness of the dyestuffsto alkalies. Substituents of this kind are} for instance, the sulfonicacid and the earboxylic acid group.-

1. The water-insoluble 'a'zo" dyestuffs of the general formula: I 1 Ywherein the nuclei R aiid fumayue substituted oo-NH OCH;

suorus'r LEQPOLDV ARTHUR ZITSCHER.

